4-(3,3-dihalo-allyloxy)phenoxy alkyl derivatives

ABSTRACT

Compounds of formula 
                         
wherein
     A 1 , A 2  and A 3  are each independently of the others a bond or a C 1 –C 6 alkylene bridge;   A 4  is a C 1 –C 6 alkylene bridge;   D is CH or N;   W is, for example, O, NR 7  or S;   T is, for example, a bond, O, NH or NR 7 ;   Q is O, NR 7 , S, SO or SO 2 ;   Y is O, NR 7 , S, SO or SO 2 ;   X 1  and X 2  are each independently of the other fluorine, chlorine or bromine;   R 1 , R 2  and R 3  are, for example, H, halogen, CN, nitro, C 1 –C 6 alkyl, C 1 –C 6 haloalkyl, C 1 –C 6 alkylcarbonyl or C 2 –C 6 alkenyl;   R 4  is, for example, H, halogen, CN, nitro or C 1 –C 6 alkyl;   R 5  and R 6  are, for example, H, CN, OH, C 1 –C 6 alkyl, C 3 –C 8 cycloalkyl, C 3 –C 8 cycloalkyl-C 1 –C 6 alkyl, C 1 –C 6 haloalkyl, C 1 –C 6 alkoxy or C 1 –C 6 haloalkoxy;   R 7  is H, C 1 –C 6 alkyl, C 1 –C 6 alkoxyalkyl or C 1 –C 6 alkylcarbonyl;   k, when D is nitrogen, is 1, 2 or 3; or, when D is CH, is 1, 2, 3 or 4; and   m is 1 or 2;   and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form,   a process for the preparation of those compounds and their use, pesticidal compositions in which the active ingredient has been selected from those compounds or an agrochemically acceptable salt thereof, a process for the preparation of those compositions and their use, plant propagation material treated with those compositions, and a method of controlling pests.

This application is a 371 of International Application No. PCT/EP03/06846 filed Jun. 27, 2003, which claims priority to CH 1123/02 filed Jun. 28, 2002, the contents of which are incorporated herein by reference.

The present invention relates (1) to compounds of formula

wherein

A₁, A₂ and A₃ are each independently of the others a bond or a C₁–C₆alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl;

A₄ is a C₁–C₆alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl;

D is CH or N;

W is O, NR₇, S, SO, SO₂, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR₈— or —NR₈—C(═O)—;

T is a bond, O, NH, NR₇, S, SO, SO₂, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR₈— or —NR₈—C(═O)—;

Q is O, NR₇, S, SO or SO₂;

Y is O, NR₇, S, SO or SO₂;

X₁ and X₂ are each independently of the other fluorine, chlorine or bromine;

R₁, R₂ and R₃ are each independently of the others H, halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₁–C₆alkoxycarbonyl or C₂–C₆haloalkenyloxy; the substituents R₃ being independent of one another when m is 2;

R₄ is H, halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₁–C₆alkoxycarbonyl or C₂–C₆haloalkenyloxy; the substituents R₄ being independent of one another when k is greater than 1;

R₅ is H, CN, OH, C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, —C(═O)R₉, —C(═S)R₉, phenyl, benzyl; or phenyl, phenylcarbonyl or benzyl each of which is substituted in the aromatic ring by from one to five identical or different substituents selected from the group consisting of halogen, C₁–C₆alkyl, halo-C₁–C₆alkyl, C₁–C₆alkoxy, halo-C₁–C₆alkoxy, hydroxy, cyano and nitro;

R₆ is H, CN, C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₆haloalkyl, —C(═O)R₉, —C(═S)R₉, phenyl, benzyl; or phenyl, phenylcarbonyl or benzyl each of which is substituted in the aromatic ring by from one to five identical or different substituents selected from the group consisting of halogen, C₁–C₆alkyl, halo-C₁–C₆alkyl, C₁–C₆alkoxy, halo-C₁–C₆alkoxy, hydroxy, cyano and nitro; or

R₅ and R₆ together form a four- to eight-membered, straight-chain or branched alkylene bridge wherein a CH₂ group may have been replaced by O, S or NR₁₀, and the alkylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl; or

R₆ is —C(═O)R₉ or —C(═S)R₉, and R₅ and R₉ together form a three- to eight-membered, straight-chain or branched alkylene bridge wherein a CH₂ group may have been replaced by O, S or NR₁₀, and the alkylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl; or

R₅ and R₆ are each independently of the other —C(═O)R₉ or —C(═S)R₉, and the two R₉ together form a two- to eight-membered, straight-chain or branched alkylene bridge wherein a CH₂ group may have been replaced by O, S or NR₁₀; and the alkylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl;

R₇ is H, C₁–C₆alkyl, C₁–C₃haloalkyl, C₁–C₃haloalkylcarbonyl, C₁–C₆alkoxyalkyl C₁–C₆alkylcarbonyl or C₃–C₈cycloalkyl;

R₈ is H, C₁–C₆alkyl, C₁–C₃haloalkyl, C₁–C₃haloalkylcarbonyl, C₁–C₆alkoxyalkyl C₁–C₆alkylcarbonyl or C₃–C₈cycloalkyl;

R₉ is C₁–C₆alkyl, C₁–C₆haloalkyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₃–C₆cycloalkyl, phenyl, benzyl; or phenyl or benzyl each of which is unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₁–C₆alkoxycarbonyl, C₁–C₃haloalkoxycarbonyl and C₂–C₆haloalkenyloxy;

R₁₀ is H, C₁–C₆alkyl, C₁–C₃haloalkyl, C₁–C₃haloalkylcarbonyl, C₁–C₆alkoxyalkyl, C₁–C₆alkylcarbonyl or C₃–C₈cycloalkyl;

k, when D is nitrogen, is 1, 2 or 3; or, when D is CH, is 1, 2, 3 or 4; and

m is 1 or 2;

and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form, to a process for the preparation of those compounds, E/Z isomers and tautomers and to their use, to pesticidal compositions in which the active ingredient has been selected from those compounds, E/Z isomers and tautomers, and to a process for the preparation of those compositions and to their use, to intermediates and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in free form or in salt form, for the preparation of those compounds, where applicable to tautomers, in free form or in salt form, of those intermediates and to a process for the preparation of those intermediates and their tautomers and to their use.

Certain dihalovinyl derivatives are proposed in the literature as active ingredients in pesticidal compositions. The biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, especially for controlling insects and members of the order Acarina, that problem being solved according to the invention by the provision of the present compounds of formula (I).

The compounds of formula (I) and, where applicable, their tautomers are able to form salts, e.g. acid addition salts. The latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, e.g. halo-substituted, C₁–C₄alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo-substituted, C₁–C₄alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid. Furthermore, compounds of formula (I) having at least one acid group are able to form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. On the one hand the free form is preferred. Of the salts of compounds of formula (I), preference is given to agrochemically advantageous salts. Hereinabove and hereinbelow any reference to the free compounds of formula (I) or to their salts is to be understood as including, where appropriate, the corresponding salts or the free compounds of formula (I), respectively. The same applies to tautomers of compounds of formula (I) and their salts.

The general terms used hereinabove and hereinbelow have the meanings given below, unless defined otherwise.

Halogen, as a group per se and as a structural element of other groups and compounds, such as haloalkyl, halocycloalkyl, haloalkenyl, haloalkynyl and haloalkoxy, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, especially chlorine.

Unless defined otherwise, carbon-containing groups and compounds each contain from 1 up to and including 20, preferably from 1 up to and including 18, especially from 1 up to and including 10, more especially from 1 up to and including 6, especially from 1 up to and including 4, especially from 1 up to and including 3, more especially 1 or 2, carbon atoms; methyl is especially preferred.

Alkylene is a straight-chain or branched bridging member and is especially —CH₂—, —CH₂CH₂—, —CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—CH₂—, —CH(CH₃)—, —CH₂(CH₃)CH₂—CH₂—, —CH(C₂H₅)—, —C(CH₃)₂—, —CH(CH₃)CH₂—, —CH(CH₃)CH(CH₃)—, or —CH₂C(CH₃)₂—CH₂—.

Alkyl, as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfonyl and alkylsulfonyloxy, is—in each case giving due consideration to the number of carbon atoms contained in the group or compound in question—either straight-chained, e.g. methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octadecyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl and alkynyl—as groups per se and as structural elements of other groups and compounds, such as haloalkenyl, haloalkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy or haloalkynyloxy—are straight-chain or branched and each contains two or preferably one unsaturated carbon-carbon bond(s). There may be mentioned by way of example vinyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, prop-2-yn-1-yl, but-2-yn-1-yl and but-3-yn-1-yl.

Cycloalkyl—as a group per se and as a structural element of other groups and compounds, such as alkyl—is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl and cyclohexyl, and especially cyclopropyl, are preferred.

Halo-substituted carbon-containing groups and compounds, such as haloalkyl and haloalkoxy, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different. Examples of haloalkyl—as a group per se and as a structural element of other groups and compounds, such as haloalkoxy—are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF₂, CF₃ or CH₂Cl; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CH₂CH₂Cl, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF₂CF₂CF₃, CH(CF₃)₂ or CH₂CH₂CH₂Cl; and butyl or an isomer thereof substituted from one to nine times by fluorine, chorine and/or bromine, such as CF(CF₃)CHFCF₃, CF₂(CF₂)₂CF₃ or CH₂(CF₂)₂CF₃.

Aryl is especially phenyl or naphthyl, preferably phenyl.

Preferred embodiments within the scope of the invention are

(2) compounds according to (1) of formula (I) wherein X₁ and X₂ are chlorine or bromine, especially chlorine;

(3) compounds according to (1) or (2) of formula (I) wherein A₁ is a bond;

(4) compounds according to (1) to (3) of formula (I) wherein the group A₂-T-A₃ is a bond;

(5) compounds according to (1) to (4) of formula (I) wherein W is oxygen, —C(═O)O— or —C(═O)NH—, especially O;

(6) compounds according to (1) to (5) of formula (I) wherein A₄ is a straight-chain alkylene bridge, especially ethylene, propylene or butylene, more especially propylene;

(7) compounds according to (1) to (6) of formula (I) wherein Q is oxygen;

(8) compounds according to (1) to (7) of formula (I) wherein Y is oxygen;

(9) compounds according to (1) to (8) of formula (I) wherein R₁ and R₂ are bromine or chlorine, especially chlorine;

(10) compounds according to (1) to (9) of formula (I) wherein R₃ is hydrogen;

(11) compounds according to (1) to (10) of formula (I) wherein R₄ is hydrogen;

(12) compounds according to (1) to (11) of formula (I) wherein R₅ is H, C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy;

(13) compounds according to (1) to (12) of formula (I) wherein R₆ is —C(═O)R₉ or —C(═S)R₉, and R₉ is C₁–C₆alkyl, C₁–C₆haloalkyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₃–C₆cycloalkyl or phenyl;

(14) compounds according to (1) to (3) and (5) to (12) of formula (I) wherein A₂ is a bond, T is oxygen and A₃ is a C₁–C₆alkylene bridge;

(15) compounds according to (1) to (3) of formula (I) wherein A₂ is a bond, T is —C(═O)O— wherein the oxygen is bonded to A₃, or is —C(═O)NH— wherein NH is bonded to A₃, and A₃ is a C₁–C₆alkylene bridge.

Special preference is given to the compounds listed in the Tables.

The invention relates also to a process for the preparation of a compound of formula (I), or a salt thereof, wherein

(a) a compound of formula

wherein A₁, A₂, A₃, A₄, D, W, Q, T, R₁, R₂, R₃, R₄, R₅, R₆, m and k are as defined for formula (I) under (1), Z₁ is —C(═O)R₁₁ and R₁₁ is H or C₁–C₆alkyl, is converted in the presence of an oxidising agent, especially a peracid, into a compound of formula G-Z_(2a)  (IIIa);

wherein Z_(2a) is O—C(═O)—R₁₂ and R₁₂ is C₁–C₆alkyl, and G denotes the part of the formula in the brackets designated G in formula (II); either

(b₁) a compound of formula (IIIa) above or of formula G-Z_(2b)  (IIIb),

wherein G denotes the part of the formula in the brackets designated G in formula (II), Z_(3b) is a radical of formula —Y—C(═O)R₁₃, W is as defined for formula (I) under (1), and R₁₃ is C₁–C₁₂alkyl unsubstituted or substituted by from one to three identical or different halogen substituents, or is phenyl unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₁–C₆alkoxycarbonyl and C₂–C₆haloalkenyloxy, is converted by hydrolytic cleavage into a compound of formula G-Z₃  (IV),

wherein G denotes the part of the formula in the brackets designated G in formula (II), Z₃ is YH, and Y is as defined for formula (I) under (1); or

(c) a compound of formula G-Z₄  (V),

wherein Z₄ is Y—CH₂-phenyl, wherein the phenyl radical is unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₁–C₆alkoxycarbonyl or C₂–C₆haloalkenyloxy, G denotes the part of the formula in the brackets designated G in formula (II), and Y is as defined for formula (I), is converted by removal of the benzyl group into a compound of formula (IV), as defined above;

(d) the compound of formula (IV) so obtained is reacted in the presence of a base with a compound of formula

wherein Hal is halogen, preferably bromine or chlorine, and alkyl is C₁–C₆alkyl, or the two alkyl radicals together form a C₃–C₈alkylene bridge, to form a compound of formula G-Z₅  (VI),

wherein G denotes the part of the formula in the brackets designated G in formula (II), and Z₅ is

wherein alkyl and Y are as defined above;

(e) the compound of formula (VI) so obtained is converted by deprotection of the acetal function in the presence of an acid into a compound of formula G-Z₆  (VII),

wherein Z₆ is a group —Y—CH₂—C(═O)H, G is as defined above for the compound of formula (II), and Y is as defined for formula (I) under (1), either

(f₁) for the preparation of a compound of formula (I) wherein X₁ and X₂ are chlorine or bromine, a compound of formula (VII) is reacted in the presence of a phosphine with a compound of formula C(X)₄ wherein X is chlorine or bromine; or

(f₂) for the preparation of a compound of formula (I) wherein X₁ and X₂ are chlorine, a compound of formula (VII) is reacted first with CCl₃—COOH or with chloroform in the presence of a strong base, then with acetic anhydride and subsequently with powdered zinc in acetic acid; or

(f₃) for the preparation of a compound of formula (I) wherein X₁ is fluorine and X₂ is chlorine or bromine, a compound of formula (VII) is reacted first with a compound of the formula CF₂X₂, of the formula CFX₃, of the formula CF₂XC(═O)ONa or of the formula CFX₂C(═O)ONa, in the presence of a phosphine; or

(g₁) for the preparation of a compound of formula (I) wherein X₁ and X₂ are chlorine or bromine, a compound of formula (IV) is reacted in the presence of base with a compound of formula

wherein L₃ is a leaving group, preferably chlorine or bromine, and Hal is chlorine or bromine; or

(g₂) for the preparation of a compound of formula (I) wherein X₁ and X₂ are chlorine or bromine, a compound of formula (IVa) or (IVb) is reacted in the presence of a base with a compound of formula

wherein Hal is halogen and X is chlorine or bromine.

The invention relates also to

(h) a process for the preparation of a compound of formula (I), as defined under (1), and wherein Q is O, NR₇ or S, and R₇ is as defined for formula (I) under (1), wherein a compound of formula

wherein A₁, A₂, A₃, A₄, D, W, T, R₄, R₅, R₆ and k are as defined for formula (I) under (1) and L₁ is a leaving group, in the presence of a base with a compound of formula

wherein R₁, R₂, R₃ and m are as defined for formula (I) under (1), Q is O, NR₇ or S and Z is one of the radicals Z₁ to Z₆ as defined for the above formulae (II) to (VII), and R₇ is as defined for formula (I) under (1), and the resulting compound of formula

wherein A₁, A₂, A₃, A₄, D, W, Q, T, R₁, R₂, R₃, R₄, R₅, R₆, m and k are as defined for formula (I) under (1) and Z is one of the radicals Z₁ to Z₆ as defined for formulae (II) to (VII) indicated above, is, as necessary, that is to say according to the meaning of the radical Z, reacted further analogously to one or more of process steps (a) to (g).

In the compounds of formulae X/a to X/f, Z in compound X/a has the same meanings as Z₁ in the compound of formula (II), and Z in compound X/b has the same meanings as Z₂ as defined for formula (III), and so on.

The invention relates also to

(i₁) a process for the preparation of a compound of formula (I) as defined above wherein W is O, NR₇, S, —O—C(═O)— or —NR₈—C(═O)—, and R₇ and R₈ are as defined for formula (I) under (1), wherein a compound of formula

wherein A₁, A₂, A₃, D, T, R₄, R₅, R₆ and k are as defined for formula (I) under (1), W₁ is O, NR₇, S or —NR₈— and R₇ is as defined for formula (I) under (1), is reacted with a compound of formula

wherein A₄, R₁, R₂, R₃, Q and m are as defined for formula (I) under (1), L₂ is a leaving group or a group Hal-C(═O)— wherein Hal is a halogen atom, preferably chlorine or bromine, and Z is one of the radicals Z₁ to Z₆ as defined in formulae (II) to (VII) indicated above; or

(i₂) for the preparation of a compound of formula (I) as defined above wherein W is O, NR₇, S, —C(═O)—O— or —C(═O)—NR₈—, and R₇ and R₈ are as defined for formula (I) under (1), wherein a compound of formula

wherein A₁, A₂, A₃, D, T, R₄, R₅, R₆ and k are as defined for formula (I) under (1), and L₁ is a leaving group or a group —C(═O)-Hal wherein Hal is a halogen atom, preferably chlorine or bromine, is reacted with a compound of formula

wherein W₂ is O, NR₇, S or NR₈, and R₇ and R₈ are as defined for formula (I) under (1),

and a resulting compound of formula (Xa) to (Xf) as defined above is, as necessary, that is to say according to the meaning of the radical Z, reacted further analogously to one or more of process steps (a) to (g).

In the compounds of formulae XII/a to XII/f and XIV/a to XIV/f, the radicals Z are as defined above for the compounds X/a to X/f; that is to say, for example, Z in the compound of formula XII/a has the same meanings as Z₁ in the compound of formula (II), and Z in compound XII/b has the same meanings as Z₂ as defined for formula (III), and so on.

The invention relates also to

(k) a process for the preparation of a compound of formula (I) as defined above under (1), wherein a compound of formula (VIII) as defined above is reacted in the presence of a base with a compound of formula

wherein R₁, R₂, R₃, Q, X₁, X₂, Y and m are as defined for formula (I) under (1).

The invention relates also to

(l) a process for the preparation of a compound of formula (I) as defined above under (1), wherein a compound of formula (XI) as defined above is reacted in a manner analogous to process variant (i) with a compound of formula

wherein A₄, R₁, R₂, R₃, Q, Y, X₁, X₂ and m are as defined for formula (I) under (1), and L₂ is as defined for formula (XII).

The compounds of formulae (IIIa) and (IIIb) wherein R₁ and R₂ are halogen can be obtained by reacting a compound of formula

wherein R₃, Q, Y and m are as defined for formula (I) under (1) with a compound of the formula Hal-C(═O)—R₁₂ wherein R₁₂ is as defined above, halogenating the resulting compound of formula

wherein R₃, Q, Y and m are as defined for formula (I) under (1), and further reacting the resulting compound of formula

wherein R₃, Q, Y and m are as defined for formula (I) under (1) and R₁ and R₂ are halogen, analogously to Process (k).

The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, if necessary, in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of approximately from −80° C. to the boiling temperature of the reaction mixture, preferably from approximately −20° C. to approximately +150° C., and, if necessary, in a closed vessel, under pressure, under an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions can be found in the Examples.

A leaving group, for example the leaving groups L₁ and L₂ defined above, or a counter-ion is to be understood hereinbefore and hereinbelow as being any removable group that customarily comes into consideration for chemical reactions, such as are known to the person skilled in the art; especially OH, halogens, such as fluorine, chlorine, bromine, iodine, —O—Si(C₁–C₈alkyl)₃, —O-aryl, —S—(C₁–C₈alkyl), —S-aryl, —O—S(═O)₂U, —S(═O)U or —S(═O)₂U, wherein U is unsubstituted or substituted C₁–C₈alkyl, C₂–C₈alkenyl, C₂–C₈alkynyl, unsubstituted or substituted aryl or unsubstituted or substituted benzyl. Especially preferred as leaving group are chlorine or bromine, mesylate, triflate, tosylate, especially chlorine; or chloride or bromide, especially chloride.

Process (a): The reaction is carried out in acetic acid or a halogenated hydrocarbon, such as dichloromethane, at temperatures of from −20° C. to 100° C., preferably at from 20° C. to 50° C. As oxidising agents there are used, for example, hydrogen peroxide, a peracid, such as peracetic acid, trifluoroperacetic acid, 3-chloroperbenzoic acid or a mixture thereof, such as sodium perborate in acetic acid.

Process (b): The reaction is preferably carried out in an alcohol, such as methanol, ethanol or an alcohol/water mixture, in the presence of an inorganic base, such as NaOH or KOH, and at temperatures of from 0° C. to 150° C., preferably from 20° C. to 80° C. Alternatively aminolysis with a primary amine, such as n-butylamine, can be carried out in a hydrocarbon, such as toluene or benzene, at temperatures of from 0° C. to 150° C., preferably at from 20° C. to 80° C.

Process (c): Depending upon the nature of the benzyl substituent to be removed, the reaction can be carried out, for example, under a hydrogen atmosphere, at a pressure of from 1 to 150 bar, especially at from 1 to 20 bar, and with the addition of a catalyst, such as palladium/carbon, in an alcohol or ether. The preferred reaction temperature is from 0° C. to 120° C., especially from 20° C. to 80° C.

Processes (d) and (g): The reaction is preferably carried out in the presence of a base, such as potassium or sodium carbonate, in acetone or dimethylformamide, at temperatures of from 0° C. to 150° C., preferably from 20° C. to 80° C. If necessary, catalytic amounts of potassium iodide or sodium iodide, or phase transfer catalysts, such as crown ethers of quaternary ammonium salts, are added.

Process (e): The reaction is preferably carried out in acetone, dichloromethane, acetic acid, or especially in water, optionally with the addition of a mineral acid, at temperatures of from 0° C. to 120° C., preferably at from 20° C. to 50° C. For complete cleavage of the acetal it is preferable to add a strong mineral acid, for example hydrochloric acid, sulfuric acid or 4-toluenesulfonic acid.

Process (f): For the preparation of the difluoro-, dichloro-, dibromo-, chlorofluoro- and bromofluoro-vinyl compounds, reaction with CCl₄, CBr₄, CF₂X₂, CFX₃, CF₂XC(═O)ONa or CFX₂C(═O)ONa wherein X is bromine or chlorine is carried out in the presence of a trialkyl- or triaryl-phosphine, optionally with the addition of powdered zinc. The reaction is carried out in an inert solvent such as, for example, benzene or toluene, or an ether, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, at temperatures of from 0° C. to 150° C., preferably at from 20° C. to 80° C.

For the preparation of the dichlorovinyl compounds it is also possible for the process to be carried out in dimethylformamide, benzene, toluene, or in an ether, at temperatures of from 0° C. to 120° C., preferably from 20° C. to 80° C., and in the presence of trichloroacetic acid/sodium trichloroacetate, then by addition of acetic anhydride, optionally with the addition of base, for example triethylamine, and finally by addition of zinc and acetic acid.

Processes (h) and (k): The reaction is preferably carried out in an ether, dimethylformamide, dimethylacetamide or N-methylpyrrolidone, at temperatures of from 0° C. to 150° C., preferably at from 20° C. to 80° C., with the addition of a base, such as potassium or sodium carbonate. Altematively a coupling reagent, for example azodicarboxylic acid diethyl or diisopropyl ester and triphenylphosphine, can be used.

Processes (i) and (l):

Where L₂ is a group Hal-C(═O)—, the process can be carried out in an inert solvent, such as in an ether or in toluene, at from 0° C. to 80° C., and in the presence of a suitable base, for example a trialkylamine.

In the other cases the reaction is carried out in an ether, in an amide, such as dimethylformamide or N-methylpyrrolidone, and at from 0° C. to 150° C. Sodium hydride, for example, can be used as base.

Compounds of formula (I) obtainable in accordance with the process or by other means can be converted into other compounds of formula (I) in a manner known per se by replacement of one or more substituents in the starting compound of formula (I) in customary manner by another (other) substituent(s) according to the invention.

In the case of such replacement, depending upon the choice of reaction conditions and starting materials suitable therefor, it is possible for only one substituent to be replaced by another substituent according to the invention in a reaction step or for a plurality of substituents to be replaced by other substituents according to the invention in the same reaction step.

Salts of compounds of formula (I) can be prepared in a manner known per se. For example, salts of compounds of formula (I) with bases are obtained by treatment of the free compounds with a suitable base or with a suitable ion exchange reagent.

Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner, for example by treatment with a suitable acid or with a suitable ion exchange reagent.

Salts of compounds of formula (I) can be converted in a manner known per se into other salts of a compound of formula (I).

The compounds of formula (I), in free form or in salt form, may be in the form of one of the possible isomers or in the form of a mixture thereof, for example, depending on the number of asymmetric carbon atoms occurring in the molecule and their absolute and relative configuration, and/or depending on the configuration of non-aromatic double bonds occurring in the molecule, in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates. The invention relates both to the pure isomers and to all possible mixtures of isomers and is to be interpreted as such hereinbefore and hereinafter, even if stereochemical details are not mentioned specifically in every case.

Mixtures of diastereoisomers, mixtures of racemates and mixtures of double bond isomers of compounds of formula (I), in free form or in salt form, which may be obtained by the process according to the invention—depending upon the starting materials and procedures chosen—or by some other method, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by means of fractional crystallisation, distillation and/or chromatography.

Mixtures of enantiomers, such as racemates, that are obtainable in a corresponding manner can be resolved into the enantiomers by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, only one enantiomer being complexed, or by conversion into diastereoisomeric salts and separation of the mixture of diastereoisomers so obtained, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be freed by the action of suitable agents.

Apart from by separation of corresponding mixtures of isomers, pure diastereoisomers or enantiomers can be obtained according to the invention also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention using starting materials having correspondingly suitable stereo-chemistry.

In each case it is advantageous to isolate or synthesise the biologically more active isomer, e.g. enantiomer or diastereoisomer, or isomeric mixture, e.g. enantiomeric mixture or diastereoisomeric mixture, where the individual components have different biological activity.

The compounds of formula (I), in free form or salt form, can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents which may have been used for the crystallisation of compounds in solid form.

The invention relates to all those embodiments of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and some or all of the remaining steps are carried out or a starting material is used in the form of a derivative or salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.

In the process of the present invention it is preferable to use those starting materials and intermediates, in each case in free form or in salt form, which result in the compounds of formula (I) and their salts described at the beginning as being especially valuable.

The invention relates especially to the preparation processes described in Examples P1 to P4.

The invention relates also to the intermediates of formulae (II) to (XIX), where novel, and, where applicable, to their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form. The preferences applying to such compounds are the same as those for the compounds of formula (I).

In the area of pest control, the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and members of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced ovi-position and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60%.

The said animal pests include, for example, those mentioned in European Patent Application EP-A-736 252, page 5, line 55, to page 6, line 55. The pests mentioned therein are therefore included by reference in the subject matter of the present invention. The active ingredients according to the invention are especially suitable for controlling Boophilus microplus, Nilaparvata lugens and Tetranychus urticae, more especially for controlling those pests in crops of vegetables, fruit and rice.

The active ingredients according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, foliage, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.

Target crops include especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g. strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.

Further areas of use of the active ingredients according to the invention are the protection of stored goods and storerooms and the protection of raw materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type

The invention therefore relates also to pesticidal compositions, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules and encapsulations in polymer substances, that comprise at least one of the active ingredients according to the invention, the choice of formulation being made in accordance with the intended objectives and the prevailing circumstances.

The active ingredient is used in those compositions in pure form, a solid active ingredient, for example, being used in a specific particle size, or preferably together with at least one of the adjuvants customary in formulation technology, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).

As formulation adjuvants there are used, for example, solid carriers, solvents, stabilisers, “slow release” adjuvants, colourings and optionally surface-active substances (surfactants). Suitable carriers and adjuvants include all substances customarily used in crop protection products, especially products for the control of slugs and snails. As adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and further adjuvants in the compositions used according to the invention, there come into consideration, for example, those described in EP-A-736 252; they are included by reference in the subject matter of the present invention.

The compositions generally comprise from 0.1 to 99%, especially from 0.1 to 95%, of active ingredient and from 1 to 99.9%, especially from 5 to 99.9%, of at least one solid or liquid adjuvant, the composition generally including from 0 to 25%, especially from 0.1 to 20%, of surfactants (%=% by weight in each case). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations having considerably lower concentrations of active ingredient. Preferred compositions have especially the following compositions (%=percent by weight):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20% solvent: 5 to 98%, preferably 70 to 85% Dusts:

active ingredient:  0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension Concentrates:

active ingredient:  5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant:  1 to 40%, preferably 2 to 30% Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier:   5 to 99%, preferably 15 to 98% Granules:

active ingredient:  0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The action of the compounds according to the invention and the compositions comprising them against animal pests can be significantly broadened and adapted to the given circumstances by the addition of other insecticides, acaricides or nematicides. Suitable additives include, for example, members of the following classes of active ingredient: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, neonicotinoids and Bacillus thuringiensis preparations.

Examples of especially suitable mixing partners include: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a compound obtainable from the Bacillus thuringiensis strain GC91 or from the strain NCTC11821; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cyhalothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb; fenvalerate; formothion; methiocarb; heptenophos; imidacloprid; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid; avermectin B₁ (abamectin); emamectin; emamectin benzoate; spinosad; a plant extract that is active against insects; a preparation that comprises nematodes and is active against insects; a preparation obtainable from Bacillus subtilis; a preparation that comprises fungi and is active against insects; a preparation that comprises viruses and is active against insects; chlorfenapyr; acephate; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; betacyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxim; butylpyridaben; cadusafos; carbaryl; carbophenothion; chloethocarb; chlorethoxyfos; chlormephos; cis-resmethrin; clocythrin; clofentezine; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos; dioxathion; edifenphos; esfenvalerate; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fernbutatin oxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion; ivermectin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemeton M; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M; pirimiphos E; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyradaphenthion; pyresmethrin; pyrethrum; tebufenozide, salithion; sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlorvinphos; thiacloprid; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarthene; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; YI 5301/5302; zetamethrin; DPX-MP062—indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylyl methylcarbamate); or the fungus pathogen Metarhizium anisopliae; more especially fipronil, thiamethoxam or lambda-cyhalothrin.

The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers as well as fertilisers or other active ingredients for obtaining special effects, e.g. acaricides, bactericides, fungicides, nematicides, molluscicides or selective herbicides.

The compositions according to the invention are prepared in known manner, in the absence of adjuvants, e.g. by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a certain particle size, and in the presence of at least one adjuvant, e.g. by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s). The invention relates likewise to such processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of such compositions.

The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and the prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

A preferred method of application in the area of crop protection is application to the foliage of the plants (foliar application), the frequency and the rate of application being dependent upon the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) when the locus of the plants is impregnated with a liquid formulation or when the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.

The compositions according to the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seed, such as fruits, tubers or grains, or plant cuttings, against animal pests. The propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown. The active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.

The following Examples serve to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius; mixing ratios of solvents are given in parts by volume.

PREPARATION EXAMPLES Example P1 Preparation of (4-{3-[2,6-dichloro-4-(3,3-dichloroallyloxy)-phenoxy]-propoxy}-phenyl)-carbamic acid tert-butyl ester

1.69 g of azadicarboxylic acid diisopropyl ester are added dropwise at 0–5° C. to a solution of 1.97 g of triphenylphosphine in 60 ml of THF. After 30 minutes at 0–5° C., 2.5 g of 3-[2,6-dichloro-4-(3,3-dichloroallyloxy)-phenoxy]-propan-1-ol and 1.5 g of (4-hydroxy-phenyl)-carbamic acid tert-butyl ester dissolved in 30 ml of tetrahydrofuran are added dropwise. After being stirred for 24 hours at room temperature, the reaction mixture is concentrated and then purified over silica gel. (4-{3-[2,6-Dichloro-4-(3,3-dichloroallyloxy)-phenoxy]-propoxy}-phenyl)-carbamic acid tert-butyl ester (compound 1.6) is obtained.

Example P2

In a manner analogous to that described above it is also possible to prepare the further compounds of Tables 2 to 28 below.

TABLE A Compounds of formula (Ia)

(Ib)

and (Ic)

No. R₉ R₅ A.1 H H A.2 methoxy H A.3 ethoxy H A.4 propoxy H A.5 butoxy H A.6 pentyloxy H A.7 hexyloxy H A.8 isopropoxy H A.9 isobutoxy H A.10 isopentyloxy H A.11 tert-butoxy H A.12 2,2-dimethylpropoxy H A.13 vinyloxy H A.14 allyloxy H A.15 propargyloxy H A.16 propen-2-yloxy H A.17 benzyloxy H A.18 4-nitrobenzyloxy H A.19 methyl H A.20 ethyl H A.21 propyl H A.22 butyl H A.23 pentyl H A.24 hexyl H A.25 isopropyl H A.26 isobutyl H A.27 isopentyl H A.28 tert-butyl H A.29 2,2-dimethylpropyl H A.30 cyclopropyl H A.31 cyclobutyl H A.32 cyclopentyl H A.33 cyclohexyl H A.34 trifluoromethyl H A.35 pentafluoroethyl H A.36 4-trifluoromethylphenyl H A.37 4-trifluoromethylbenzyl H A.38 2-chloro-(1-chloromethyl-1-methyl)-ethyl H A.39 2-chloro-1,1-dimethyl-ethyl H A.40 H methyl A.41 methoxy methyl A.42 ethoxy methyl A.43 propoxy methyl A.44 butoxy methyl A.45 pentyloxy methyl A.46 hexyloxy methyl A.47 isopropoxy methyl A.48 isobutoxy methyl A.49 isopentyloxy methyl A.50 tert-butoxy methyl A.51 2,2-dimethylpropoxy methyl A.52 vinyloxy methyl A.53 allyloxy methyl A.54 propargyloxy methyl A.55 propen-2-yloxy methyl A.56 benzyloxy methyl A.57 4-nitrobenzyloxy methyl A.58 methyl methyl A.59 ethyl methyl A.60 propyl methyl A.61 butyl methyl A.62 pentyl methyl A.63 hexyl methyl A.64 isopropyl methyl A.65 isobutyl methyl A.66 isopentyl methyl A.67 tert-butyl methyl A.68 2,2-dimethylpropyl methyl A.69 cyclopropyl methyl A.70 cyclobutyl methyl A.71 cyclopentyl methyl A.72 cyclohexyl methyl A.73 trifluoromethyl methyl A.74 pentafluoroethyl methyl A.75 4-trifluoromethylphenyl methyl A.76 4-trifluoromethylbenzyl methyl A.77 2-chloro-(1-chloromethyl-1-methyl)-ethyl methyl A.78 2-chloro-1,1-dimethyl-ethyl methyl A.79 H ethyl A.80 methoxy ethyl A.81 ethoxy ethyl A.82 propoxy ethyl A.83 butoxy ethyl A.84 pentyloxy ethyl A.85 hexyloxy ethyl A.86 isopropoxy ethyl A.87 isobutoxy ethyl A.88 isopentyloxy ethyl A.89 tert-butoxy ethyl A.90 2,2-dimethylpropoxy ethyl A.91 vinyloxy ethyl A.92 allyloxy ethyl A.93 propargyloxy ethyl A.94 propen-2-yloxy ethyl A.95 benzyloxy ethyl A.96 4-nitrobenzyloxy ethyl A.97 methyl ethyl A.98 ethyl ethyl A.99 propyl ethyl A.100 butyl ethyl A.101 pentyl ethyl A.102 hexyl ethyl A.103 isopropyl ethyl A.104 isobutyl ethyl A.105 isopentyl ethyl A.106 tert-butyl ethyl A.107 2,2-dimethylpropyl ethyl A.108 cyclopropyl ethyl A.109 cyclobutyl ethyl A.110 cyclopentyl ethyl A.111 cyclohexyl ethyl A.112 trifluoromethyl ethyl A.113 pentafluoroethyl ethyl A.114 4-trifluoromethylphenyl ethyl A.115 4-trifluoromethylbenzyl ethyl A.116 2-chloro-(1-chloromethyl-1-methyl)-ethyl ethyl A.117 2-chloro-1,1-dimethyl-ethyl ethyl A.118 H propyl A.119 methoxy propyl A.120 ethoxy propyl A.121 propoxy propyl A.122 butoxy propyl A.123 pentyloxy propyl A.124 hexyloxy propyl A.125 isopropoxy propyl A.126 isobutoxy propyl A.127 isopentyloxy propyl A.128 tert-butoxy propyl A.129 2,2-dimethylpropoxy propyl A.130 vinyloxy propyl A.131 allyloxy propyl A.132 propargyloxy propyl A.133 propen-2-yloxy propyl A.134 benzyloxy propyl A.135 4-nitrobenzyloxy propyl A.136 methyl propyl A.137 ethyl propyl A.138 propyl propyl A.139 butyl propyl A.140 pentyl propyl A.141 hexyl propyl A.142 isopropyl propyl A.143 isobutyl propyl A.144 isopentyl propyl A.145 tert-butyl propyl A.146 2,2-dimethylpropyl propyl A.147 cyclopropyl propyl A.148 cyclobutyl propyl A.149 cyclopentyl propyl A.150 cyclohexyl propyl A.151 trifluoromethyl propyl A.152 pentafluoroethyl propyl A.153 4-trifluoromethylphenyl propyl A.154 4-trifluoromethylbenzyl propyl A.155 2-chloro-(1-chloromethyl-1-methyl)-ethyl propyl A.156 2-chloro-1,1-dimethyl-ethyl propyl A.157 H allyl A.158 methoxy allyl A.159 ethoxy allyl A.160 propoxy allyl A.161 butoxy allyl A.162 pentyloxy allyl A.163 hexyloxy allyl A.164 isopropoxy allyl A.165 isobutoxy allyl A.166 isopentyloxy allyl A.167 tert-butoxy allyl A.168 2,2-dimethylpropoxy allyl A.169 vinyloxy allyl A.170 allyloxy allyl A.171 propargyloxy allyl A.172 propen-2-yloxy allyl A.173 benzyloxy allyl A.174 4-nitrobenzyloxy allyl A.175 methyl allyl A.176 ethyl allyl A.177 propyl allyl A.178 butyl allyl A.179 pentyl allyl A.180 hexyl allyl A.181 isopropyl allyl A.182 isobutyl allyl A.183 isopentyl allyl A.184 tert-butyl allyl A.185 2,2-dimethylpropyl allyl A.186 cyclopropyl allyl A.187 cyclobutyl allyl A.188 cyclopentyl allyl A.189 cyclohexyl allyl A.190 trifluoromethyl allyl A.191 pentafluoroethyl allyl A.192 4-trifluoromethylphenyl allyl A.193 4-trifluoromethylbenzyl allyl A.194 2-chloro-(1-chloromethyl-1-methyl)-ethyl allyl A.195 2-chloro-1,1-dimethyl-ethyl allyl A.196 H propargyl A.197 methoxy propargyl A.198 ethoxy propargyl A.199 propoxy propargyl A.200 butoxy propargyl A.201 pentyloxy propargyl A.202 hexyloxy propargyl A.203 isopropoxy propargyl A.204 isobutoxy propargyl A.205 isopentyloxy propargyl A.206 tert-butoxy propargyl A.207 2,2-dimethylpropoxy propargyl A.208 vinyloxy propargyl A.209 allyloxy propargyl A.210 propargyloxy propargyl A.211 propen-2-yloxy propargyl A.212 benzyloxy propargyl A.213 4-nitrobenzyloxy propargyl A.214 methyl propargyl A.215 ethyl propargyl A.216 propyl propargyl A.217 butyl propargyl A.218 pentyl propargyl A.219 hexyl propargyl A.220 isopropyl propargyl A.221 isobutyl propargyl A.222 isopentyl propargyl A.223 tert-butyl propargyl A.224 2,2-dimethylpropyl propargyl A.225 cyclopropyl propargyl A.226 cyclobutyl propargyl A.227 cyclopentyl propargyl A.228 cyclohexyl propargyl A.229 trifluoromethyl propargyl A.230 pentafluoroethyl propargyl A.231 4-trifluoromethylphenyl propargyl A.232 4-trifluoromethylbenzyl propargyl A.233 2-chloro-(1-chloromethyl-1-methyl)-ethyl propargyl A.234 2-chloro-1,1-dimethyl-ethyl propargyl A.235 H methoxy A.236 methoxy methoxy A.237 ethoxy methoxy A.238 propoxy methoxy A.239 butoxy methoxy A.240 pentyloxy methoxy A.241 hexyloxy methoxy A.242 isopropoxy methoxy A.243 isobutoxy methoxy A.244 isopentyloxy methoxy A.245 tert-butoxy methoxy A.246 2,2-dimethylpropoxy methoxy A.247 vinyloxy methoxy A.248 allyloxy methoxy A.249 propargyloxy methoxy A.250 propen-2-yloxy methoxy A.251 benzyloxy methoxy A.252 4-nitrobenzyloxy methoxy A.253 methyl methoxy A.254 ethyl methoxy A.255 propyl methoxy A.256 butyl methoxy A.257 pentyl methoxy A.258 hexyl methoxy A.259 isopropyl methoxy A.260 isobutyl methoxy A.261 isopentyl methoxy A.262 tert-butyl methoxy A.263 2,2-dimethylpropyl methoxy A.264 cyclopropyl methoxy A.265 cyclobutyl methoxy A.266 cyclopentyl methoxy A.267 cyclohexyl methoxy A.268 trifluoromethyl methoxy A.269 pentafluoroethyl methoxy A.270 4-trifluoromethylphenyl methoxy A.271 4-trifluoromethylbenzyl methoxy A.272 2-chloro-(1-chloromethyl-1-methyl)-ethyl methoxy A.273 2-chloro-1,1-dimethyl-ethyl methoxy A.274 H ethoxy A.275 methoxy ethoxy A.276 ethoxy ethoxy A.277 propoxy ethoxy A.278 butoxy ethoxy A.279 pentyloxy ethoxy A.280 hexyloxy ethoxy A.281 isopropoxy ethoxy A.282 isobutoxy ethoxy A.283 isopentyloxy ethoxy A.284 tert-butoxy ethoxy A.285 2,2-dimethylpropoxy ethoxy A.286 vinyloxy ethoxy A.287 allyloxy ethoxy A.288 propargyloxy ethoxy A.289 propen-2-yloxy ethoxy A.290 benzyloxy ethoxy A.291 4-nitrobenzyloxy ethoxy A.292 methyl ethoxy A.293 ethyl ethoxy A.294 propyl ethoxy A.295 butyl ethoxy A.296 pentyl ethoxy A.297 hexyl ethoxy A.298 isopropyl ethoxy A.299 isobutyl ethoxy A.300 isopentyl ethoxy A.301 tert-butyl ethoxy A.302 2,2-dimethylpropyl ethoxy A.303 cyclopropyl ethoxy A.304 cyclobutyl ethoxy A.305 cyclopentyl ethoxy A.306 cyclohexyl ethoxy A.307 trifluoromethyl ethoxy A.308 pentafluoroethyl ethoxy A.309 4-trifluoromethylphenyl ethoxy A.310 4-trifluoromethylbenzyl ethoxy A.311 2-chloro-(1-chloromethyl-1-methyl)-ethyl ethoxy A.312 2-chloro-1,1-dimethyl-ethyl ethoxy A.313 H methylcarbonyl A.314 methoxy methylcarbonyl A.315 ethoxy methylcarbonyl A.316 propoxy methylcarbonyl A.317 butoxy methylcarbonyl A.318 pentyloxy methylcarbonyl A.319 hexyloxy methylcarbonyl A.320 isopropoxy methylcarbonyl A.321 isobutoxy methylcarbonyl A.322 isopentyloxy methylcarbonyl A.323 tert-butoxy methylcarbonyl A.324 2,2-dimethylpropoxy methylcarbonyl A.325 vinyloxy methylcarbonyl A.326 allyloxy methylcarbonyl A.327 propargyloxy methylcarbonyl A.328 propen-2-yloxy methylcarbonyl A.329 benzyloxy methylcarbonyl A.330 4-nitrobenzyloxy methylcarbonyl A.331 methyl methylcarbonyl A.332 ethyl methylcarbonyl A.333 propyl methylcarbonyl A.334 butyl methylcarbonyl A.335 pentyl methylcarbonyl A.336 hexyl methylcarbonyl A.337 isopropyl methylcarbonyl A.338 isobutyl methylcarbonyl A.339 isopentyl methylcarbonyl A.340 tert-butyl methylcarbonyl A.341 2,2-dimethylpropyl methylcarbonyl A.342 cyclopropyl methylcarbonyl A.343 cyclobutyl methylcarbonyl A.344 cyclopentyl methylcarbonyl A.345 cyclohexyl methylcarbonyl A.346 trifluoromethyl methylcarbonyl A.347 pentafluoroethyl methylcarbonyl A.348 4-trifluoromethylphenyl methylcarbonyl A.349 4-trifluoromethylbenzyl methylcarbonyl A.350 2-chloro-(1-chloromethyl-1-methyl)-ethyl methylcarbonyl A.351 2-chloro-1,1-dimethyl-ethyl methylcarbonyl A.352 H ethylcarbonyl A.353 methoxy ethylcarbonyl A.354 ethoxy ethylcarbonyl A.355 propoxy ethylcarbonyl A.356 butoxy ethylcarbonyl A.357 pentyloxy ethylcarbonyl A.358 hexyloxy ethylcarbonyl A.359 isopropoxy ethylcarbonyl A.360 isobutoxy ethylcarbonyl A.361 isopentyloxy ethylcarbonyl A.362 tert-butoxy ethylcarbonyl A.363 2,2-dimethylpropoxy ethylcarbonyl A.364 vinyloxy ethylcarbonyl A.365 allyloxy ethylcarbonyl A.366 propargyloxy ethylcarbonyl A.367 propen-2-yloxy ethylcarbonyl A.368 benzyloxy ethylcarbonyl A.369 4-nitrobenzyloxy ethylcarbonyl A.370 methyl ethylcarbonyl A.371 ethyl ethylcarbonyl A.372 propyl ethylcarbonyl A.373 butyl ethylcarbonyl A.374 pentyl ethylcarbonyl A.375 hexyl ethylcarbonyl A.376 isopropyl ethylcarbonyl A.377 isobutyl ethylcarbonyl A.378 isopentyl ethylcarbonyl A.379 tert-butyl ethylcarbonyl A.380 2,2-dimethylpropyl ethylcarbonyl A.381 cyclopropyl ethylcarbonyl A.382 cyclobutyl ethylcarbonyl A.383 cyclopentyl ethylcarbonyl A.384 cyclohexyl ethylcarbonyl A.385 trifluoromethyl ethylcarbonyl A.386 pentafluoroethyl ethylcarbonyl A.387 4-trifluoromethylphenyl ethylcarbonyl A.388 4-trifluoromethylbenzyl ethylcarbonyl A.389 2-chloro-(1-chloromethyl-1-methyl)-ethyl ethylcarbonyl A.390 2-chloro-1,1-dimethyl-ethyl ethylcarbonyl A.391 H cyclopropylcarbonyl A.392 methoxy cyclopropylcarbonyl A.393 ethoxy cyclopropylcarbonyl A.394 propoxy cyclopropylcarbonyl A.395 butoxy cyclopropylcarbonyl A.396 pentyloxy cyclopropylcarbonyl A.397 hexyloxy cyciopropylcarbonyl A.398 isopropoxy cyclopropylcarbonyl A.399 isobutoxy cyclopropylcarbonyl A.400 isopentyloxy cyclopropylcarbonyl A.401 tert-butoxy cyclopropylcarbonyl A.402 2,2-dimethylpropoxy cyclopropylcarbonyl A.403 vinyloxy cyclopropylcarbonyl A.404 allyloxy cyclopropylcarbonyl A.405 propargyloxy cyclopropylcarbonyl A.406 propen-2-yloxy cyclopropylcarbonyl A.407 benzyloxy cyclopropylcarbonyl A.408 4-nitrobenzyloxy cyclopropylcarbonyl A.409 methyl cyclopropylcarbonyl A.410 ethyl cyclopropylcarbonyl A.411 propyl cyclopropylcarbonyl A.412 butyl cyclopropylcarbonyl A.413 pentyl cyclopropylcarbonyl A.414 hexyl cyclopropylcarbonyl A.415 isopropyl cyclopropylcarbonyl A.416 isobutyl cyclopropylcarbonyl A.417 isopentyl cyclopropylcarbonyl A.418 tert-butyl cyclopropylcarbonyl A.419 2,2-dimethylpropyl cyclopropylcarbonyl A.420 cyclopropyl cyclopropylcarbonyl A.421 cyclobutyl cyclopropylcarbonyl A.422 cyclopentyl cyclopropylcarbonyl A.423 cyclohexyl cyclopropylcarbonyl A.424 trifluoromethyl cyclopropylcarbonyl A.425 pentafluoroethyl cyclopropylcarbonyl A.426 4-trifluoromethylphenyl cyclopropylcarbonyl A.427 4-trifluoromethylbenzyl cyclopropylcarbonyl A.428 2-chloro-(1-chloromethyl-1-methyl)-ethyl cyclopropylcarbonyl A.429 2-chloro-1,1-dimethyl-ethyl cyclopropylcarbonyl A.430 H methoxycarbonyl A.431 methoxy methoxycarbonyl A.432 ethoxy methoxycarbonyl A.433 propoxy methoxycarbonyl A.434 butoxy methoxycarbonyl A.435 pentyloxy methoxycarbonyl A.436 hexyloxy methoxycarbonyl A.437 isopropoxy methoxycarbonyl A.438 isobutoxy methoxycarbonyl A.439 isopentyloxy methoxycarbonyl A.440 tert-butoxy methoxycarbonyl A.441 2,2-dimethylpropoxy methoxycarbonyl A.442 vinyloxy methoxycarbonyl A.443 allyloxy methoxycarbonyl A.444 propargyloxy methoxycarbonyl A.445 propen-2-yloxy methoxycarbonyl A.446 benzyloxy methoxycarbonyl A.447 4-nitrobenzyloxy methoxycarbonyl A.448 methyl methoxycarbonyl A.449 ethyl methoxycarbonyl A.450 propyl methoxycarbonyl A.451 butyl methoxycarbonyl A.452 pentyl methoxycarbonyl A.453 hexyl methoxycarbonyl A.454 isopropyl methoxycarbonyl A.455 isobutyl methoxycarbonyl A.456 isopentyl methoxycarbonyl A.457 tert-butyl methoxycarbonyl A.458 2,2-dimethylpropyl methoxycarbonyl A.459 cyclopropyl methoxycarbonyl A.460 cyclobutyl methoxycarbonyl A.461 cyclopentyl methoxycarbonyl A.462 cyclohexyl methoxycarbonyl A.463 trifluoromethyl methoxycarbonyl A.464 pentafluoroethyl methoxycarbonyl A.465 4-trifluoromethylphenyl methoxycarbonyl A.466 4-trifluoromethylbenzyl methoxycarbonyl A.467 2-chloro-(1-chloromethyl-1-methyl)-ethyl methoxycarbonyl A.468 2-chloro-1,1-dimethyl-ethyl methoxycarbonyl A.469 H ethoxycarbonyl A.470 methoxy ethoxycarbonyl A.471 ethoxy ethoxycarbonyl A.472 propoxy ethoxycarbonyl A.473 butoxy ethoxycarbonyl A.474 pentyloxy ethoxycarbonyl A.475 hexyloxy ethoxycarbonyl A.476 isopropoxy ethoxycarbonyl A.477 isobutoxy ethoxycarbonyl A.478 isopentyloxy ethoxycarbonyl A.479 tert-butoxy ethoxycarbonyl A.480 2,2-dimethylpropoxy ethoxycarbonyl A.481 vinyloxy ethoxycarbonyl A.482 allyloxy ethoxycarbonyl A.483 propargyloxy ethoxycarbonyl A.484 propen-2-yloxy ethoxycarbonyl A.485 benzyloxy ethoxycarbonyl A.486 4-nitrobenzyloxy ethoxycarbonyl A.487 methyl ethoxycarbonyl A.488 ethyl ethoxycarbonyl A.489 propyl ethoxycarbonyl A.490 butyl ethoxycarbonyl A.491 pentyl ethoxycarbonyl A.492 hexyl ethoxycarbonyl A.493 isopropyl ethoxycarbonyl A.494 isobutyl ethoxycarbonyl A.495 isopentyl ethoxycarbonyl A.496 tert-butyl ethoxycarbonyl A.497 2,2-dimethylpropyl ethoxycarbonyl A.498 cyclopropyl ethoxycarbonyl A.499 cyclobutyl ethoxycarbonyl A.500 cyclopentyl ethoxycarbonyl A.501 cyclohexyl ethoxycarbonyl A.502 trifluoromethyl ethoxycarbonyl A.503 pentafluoroethyl ethoxycarbonyl A.504 4-trifluoromethylphenyl ethoxycarbonyl A.505 4-trifluoromethylbenzyl ethoxycarbonyl A.506 2-chloro-(1-chloromethyl-1-methyl)-ethyl ethoxycarbonyl A.507 2-chloro-1,1-dimethyl-ethyl ethoxycarbonyl

TABLE 1 Compounds of formula

No. R₅ R₆ ¹H-NMR (CDCl₃) 300 MHz 1.1 H H 2.26 (m, 2H), 3.40 (s, NH₂), 4.10–4.22 (m, 6H), 4.59 (d, 2H), 6.12 (t, 1H), 6.63 (d, 2H), 6.78 (d, 2H), 6.82 (s, 2H) 1.2 methyl methyl 2.26 (m, 2H), 2.88 (s, 6H) 4.10–4.22 (m, 4H), 4.58 (d, 2H), 6.10 (t, 1H), 6.74 (d, 2H), 6.82 (s, 2H), 6.88 (d, 2H) 1.3 methoxycarbonyl H 2.28 (m, 2H), 3.76 (s, 3H), 4.13 (t, 2H), 4.22 (t, 2H), 4.58 (d, 2H), 6.10 (t, 1H), 6.50 (s, NH), 6.82 (s, 2H), 6.88 (d, 2H), 7.28 (d, 2H) 1.4 ethoxycarbonyl H 1.31 (t, 3H), 2.28 (m, 2H), 4.17 (t, 2H), 4.20–4.30 (t, 2H + q, 2H), 4.58 (d, 2H), 6.12 (t, 1H), 6.47 (s, NH), 6.85 (s, 2H), 6.88 (d, 2H), 7.28 (d, 2H) 1.5 isopropoxycarbonyl H 1.30 (d, 6H), 2.28 (m, 2H), 4.15 (t, 2H), 4.23 (t, 2H), 4.58 (d, 2H), 5.02 (m, 1H), 6.11 (t, 1H), 6.40 (s, NH), 6.85 (s, 2H), 6.89 (d, 2H), 7.28 (d, 2H) 1.6 tert-butyloxy- H 1.50 (s, 9H), 2.28 (m, 2H), 4.13 carbonyl (t, 2H), 4.21 (t, 2H), 4.58 (d, 2H), 6.12 (t, 1H), 6.37 (s, NH), 6.82 (s, 2H), 6.88 (d, 2H), 7.28 (d, 2H) 1.7 2,2-dimethyl- H 0.98 (s, 9H), 2.29 (m, 2H), 3.38 (s, propyloxycarbonyl 2H), 4.16 (t, 2H), 4.23 (t, 2H), 4.58 (d, 2H), 6.11 (t, 1H), 6.50 (s, NH), 6.82 (s, 2H), 6.89 (d, 2H), 7.28 (d, 2H) 1.8 vinyloxycarbonyl H 2.29 (m, 2H), 4.17 (t, 2H), 4.24 (t, 2H), 4.52 (d, 1H), 4.58 (d, 2H) 4.83 (d, 1H), 6.12 (t, 1H), 6.63 (s, NH), 6.86 (s, 2H), 6.92 (d, 2H), 7.25–7.37 (m, 2H + 1H) 1.9 allyloxycarbonyl H 2.29 (m, 2H), 4.17 (t, 2H), 4.23 (t, 2H), 4.59 (d, 2H) 4.66 (d, 2H), 5.27 (d, 1H), 5.37 (d, 1H) 5.9–6.09 (m, 1H), 6.12 (t, 1H), 6.51 (s, NH), 6.85 (s, 2H), 6.90 (d, 2H), 7.29 (d, 2H) 1.10 propargyloxy- H 2.28 (m, 2H), 2.51 (s, 1H), 4.15 carbonyl (t, 2H), 4.25 (t, 2H), 4.60 (d, 2H), 4.80 (s, 2H), 6.11 (t, 1H), 6.63 (s, NH), 6.88 (s, 2H), 6.90 (d, 2H), 7.30 (d, 2H) 1.11 propen-2-yloxy- H 2.00 (s, 3H), 2.29 (m, 2H), 4.17 (t, carbonyl 2H), 4.23 (t, 2H), 4.52 (dd, 1H), 4.49 (d, 2H) 4.72 (s, 1H), 4.80 (s, 1H) 6.12 (t, 1H), 6.60 (s, NH), 6.83 (s, 2H), 6.91 (d, 2H), 7.32 (d, 2H) 1.12 benzyloxycarbonyl H 2.28 (m, 2H), 4.17 (t, 2H), 4.25 (t, 2H), 4.60 (d, 2H), 5.19 (s, 2H), 6.12 (t, 1H), 6.54 (s, NH), 6.83 (s, 2H), 6.90 (d, 2H), 7.28–7.45 (m, 7H) 1.13 4-nitrobenzyloxy- H 2.28 (m, 2H), 4.13 (t, 2H), 4.23 (t, carbonyl 2H), 4.59 (d, 2H), 5.30 (s, 2H), 6.12 (t, 1H), 6.62 (s, NH), 6.83 (s, 2H), 6.90 (d, 2H), 7.39 (d, 2H), 7.57 (d, 2H), 8.23 (d, 2H) 1.14 methylcarbonyl H 2.18 (s, 3H), 2.29 (m, 2H), 4.13 (t, 2H), 4.23 (t, 2H), 4.58 (d, 2H), 6.12 (t, 1H), 6.83 (s, 2H), 6.90 (d, 2H), 7.03 (s, NH), 7.40 (d, 2H) 1.15 4-trifluoromethyl- 2.39 (m, 2H), 4.17 (t, 2H), 4.28 (t, carbonyl 2H), 4.58 (d, 2H), 6.12 (t, 1H), 6.83 (s, 2H), 6.94 (d, 2H), 7.47 (d, 2H), 7.79 (s, NH) 1.16 4-trifluoromethyl- H 2.29 (m, 2H), 4.16 (t, 2H), 4.28 (t, phenyl-carbonyl 2H), 4.58 (d, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 6.93 (d, 2H), 7.53 (d, 2H), 7.72 (d, 2H), 7.88 (s, NH), 7.98 (d, 2H) 1.17 4-trifluoromethyl- H 2.25 (m, 2H), 3.77 (s, 2H), 4.13 (t, benzyl-carbonyl 2H), 4.21 (t, 2H), 4.58 (d, 2H), 6.11 (t, 1H), 6.82 (s, 2H), 6.87 (d, 2H), 7.18 (s, NH), 7.33 (d, 2H), 7.48 (d, 2H), 7.63 (d, 2H) 1.18 2-chloro-1,1-di- H 1.40 (s, 6H), 2.29 (m, 2H), 3.70 (s, methyl-ethyl- 2H), 4.13 (t, 2H), 4.23 (t, 2H), carbonyl 4.57 (d, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 6.90 (d, 2H), 7.37–7.45 (d, 2H + s, NH)

Table 2: Compounds of general formula (Ia) wherein X₁ and X₂ are fluorine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 3: Compounds of general formula (Ib) wherein X₁ and X₂ are fluorine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 4: Compounds of general formula (Ic) wherein X₁ and X₂ are fluorine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 5: Compounds of general formula (Ia) wherein X₁ and X₂ are fluorine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 6: Compounds of general formula (Ib) wherein X₁ and X₂ are fluorine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 7: Compounds of general formula (Ic) wherein X₁ and X₂ are fluorine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 8: Compounds of general formula (Ia) wherein X₁ and X₂ are fluorine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 9: Compounds of general formula (Ib) wherein X₁ and X₂ are fluorine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 10: Compounds of general formula (Ic) wherein X₁ and X₂ are fluorine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 11: Compounds of general formula (Ia) wherein X₁ and X₂ are chlorine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 12: Compounds of general formula (Ib) wherein X₁ and X₂ are chlorine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 13: Compounds of general formula (Ic) wherein X₁ and X₂ are chlorine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 14: Compounds of general formula (Ia) wherein X₁ and X₂ are chlorine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 15: Compounds of general formula (Ib) wherein X₁ and X₂ are chlorine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 16: Compounds of general formula (Ic) wherein X₁ and X₂ are chlorine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 17: Compounds of general formula (Ia) wherein X₁ and X₂ are chlorine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 18: Compounds of general formula (Ib) wherein X₁ and X₂ are chlorine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 19: Compounds of general formula (Ic) wherein X₁ and X₂ are chlorine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 20: Compounds of general formula (Ia) wherein X₁ and X₂ are bromine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 21: Compounds of general formula (Ib) wherein X₁ and X₂ are bromine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 22: Compounds of general formula (Ic) wherein X₁ and X₂ are bromine and n is 2, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 23: Compounds of general formula (Ia) wherein X₁ and X₂ are bromine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 24: Compounds of general formula (Ib) wherein X₁ and X₂ are bromine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 25: Compounds of general formula (Ic) wherein X₁ and X₂ are bromine and n is 3, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 26: Compounds of general formula (Ia) wherein X₁ and X₂ are bromine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 27: Compounds of general formula (Ib) wherein X₁ and X₂ are bromine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Table 28: Compounds of general formula (Ic) wherein X₁ and X₂ are bromine and n is 4, and the combination of substituents R₅ and R₉ for each compound corresponds to a line A.1 to A.507 of Table A.

Preparation Example P3 Preparation of 3-(4-{3-[2,6-dichloro-4-(3,3-dichloroallyloxy)-phenoxy]-propoxy}-phenyl)-oxazolidin-2-one

7 mg of copper(I) iodide, 2 mg of ethylenediamine and 155 mg of tripotassium phosphate are added, under argon, to a solution of 200 mg of 1,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[3-(4-iodophenoxy)-propoxy]-benzene and 38 mg of 2-oxazolidinone in 4 ml of dioxane. After 17 hours at 110° C. the reaction mixture is filtered and concentrated. Purification over silica gel yields the title compound (compound 29.3).

Example P4

In a manner analogous to that described above it is also possible to prepare the further compounds of Tables 29 to 56 below.

TABLE 29 Compounds of formula

No. R ¹H-NMR (CDCl₃) 300 MHz 29.1

2.13 (m, 2H), 2.28 (m, 2H), 2.59 (t, 2H), 3.82(t, 2H), 4.14 (t, 2H), 4.25 (t, 2H), 4.58 (d, 2H),6.11 (t, 1H), 6.82 (s, 2H), 6.92 (d, 2H),7.50 (d, 2H) 29.2

2.29 (m, 2H), 2.89 (s, 4H), 4.13 (t, 2H), 4.28 (t,2H), 4.58 (d, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 7.01(d, 2H), 7.18 (d, 2H) 29.3

2.29 (m, 2H), 4.02 (t, 2H), 4.15 (t, 2H), 4.25 (t,2H), 4.47 (t, 2H), 4.58 (d, 2H), 6.11 (t, 1H), 6.82(s, 2H), 6.93 (d, 2H), 7.43 (d, 2H)

TABLE B Compounds of formulae (Id)

(Ie)

and (If)

No. R B.1 3-(oxazolidin)-yl-2-one B.2 3-(4-methyl-oxazolidin)-yl-2-one B.3 3-(4-ethyl-oxazolidin)-yl-2-one B.4 3-(4-propyl-oxazolidin)-yl-2-one B.5 3-(4,4-dimethyl-oxazolidin)-yl-2-one B.6 3-(4,4-diethyl-oxazolidin)-yl-2-one B.7 3-(5-methyl-oxazolidin)-yl-2-one B.8 3-(5-ethyl-oxazolidin)-yl-2-one B.9 3-(5-propyl-oxazolidin)-yl-2-one B.10 3-(5-cyclopropyl-oxazolidinone B.11 3-(5-isopropyl-oxazolidin)-yl-2-one B.12 3-(5-isobutyl-oxazolidin)-yl-2-one B.13 3-(5-allyl-oxazolidin)-yl-2-one B.14 3-(5-methoxymethyl-oxazolidin)-yl-2-one B.15 3-(5-ethoxymethyl-oxazolidin)-yl-2-one B.16 3-(5-propoxymethyl-oxazolidin)-yl-2-one B.17 3-(5-cyclopropoxymethyl-oxazolidin)-yl-2-one B.18 3-(5-isopropoxymethyl-oxazolidin)-yl-2-one B.19 3-(5-isobutoxymethyl-oxazolidin)-yl-2-one B.20 3-(5-allyloxymethyl-oxazolidin)-yl-2-one B.21 3-(5-propargyloxymethyl-oxazolidin)-yl-2-one B.22 3-(5,5-dimethyl-oxazolidin)-yl-2-one B.23 3-(5,5-diethyl-oxazolidin)-yl-2-one B.24 1-(pyrrolidin)-yl-2-one B.25 1-(3-methyl-pyrrolidin)-yl-2-one B.26 1-(3-ethyl-pyrrolidin)-yl-2-one B.27 1-(3-propyl-pyrrolidin)-yl-2-one B.28 1-(3-cyclopropyl-pyrrolidin)-yl-2-one B.29 1-(3-isopropyl-pyrrolidin)-yl-2-one B.30 1-(3-isobutyl-pyrrolidin)-yl-2-one B.31 1-(3-allyl-pyrrolidin)-yl-2-one B.32 1-(3-methoxymethyl-pyrrolidin)-yl-2-one B.33 1-(3-ethoxymethyl-pyrrolidin)-yl-2-one B.34 1-(3-propoxymethyl-pyrrolidin)-yl-2-one B.35 1-(3-cyclopropoxymethyl-pyrrolidin)-yl-2-one B.36 1-(3-isopropoxymethyl-pyrrolidin)-yl-2-one B.37 1-(3-isobutoxymethyl-pyrrolidin)-yl-2-one B.38 1-(3-allyloxymethyl-pyrrolidin)-yl-2-one B.39 1-(3,3-dimethyl-pyrrolidin)-yl-2-one B.40 1-(3,3-diethyl-pyrrolidin)-yl-2-one B.41 1-(5-methyl-pyrrolidin)-yl-2-one B.42 1-(5-ethyl-pyrrolidin)-yl-2-one B.43 1-(5-propyl-pyrrolidin-2-one B.44 1-(5-cyclopropyl-pyrrolidin)-yl-2-one B.45 1-(5-isopropyl-pyrrolidin)-yl-2-one B.46 1-(5-isobutyl-pyrrolidin)-yl-2-one B.47 1-(5-allyl-pyrrolidin)-yl-2-one B.48 1-(5-methoxymethyl-pyrrolidin)-yl-2-one B.49 1-(5-ethoxymethyl-pyrrolidin)-yl-2-one B.50 1-(5-propoxymethyl-pyrrolidin)-yl-2-one B.51 1-(5-cyclopropoxymethyl-pyrrolidin)-yl-2-one B.52 1-(5-isopropoxymethyl-pyrrolidin)-yl-2-one B.53 1-(5-isobutoxymethyl-pyrrolidin)-yl-2-one B.54 1-(5-allyloxymethyl-pyrrolidin)-yl-2-one B.55 1-(5,5-dimethyl-pyrrolidin)-yl-2-one B.56 1-(5,5-diethyl-pyrrolidin)-yl-2-one B.57 1-(pyrrolidin)-yl-2,5-dione B.58 1-(3-methyl-pyrrolidin)-yl-2,5-dione B.59 1-(3-ethyl-pyrrolidin)-yl-2,5-dione B.60 1-(3-propyl-pyrrolidin)-yl-2,5-dione B.61 1-(3-cyclopropyl-pyrrolidin)-yl-2,5-dione B.62 1-(3-isopropyl-pyrrolidin)-yl-2,5-dione B.63 1-(3-isobutyl-pyrrolidin)-yl-2,5-dione B.64 1-(3-allyl-pyrrolidin)-yl-2,5-dione B.65 1-(3-methoxymethyl-pyrrolidin)-yl-2,5-dione B.66 1-(3-ethoxymethyl-pyrrolidin)-yl-2,5-dione B.67 1-(3-propoxymethyl-pyrrolidin)-yl-2,5-dione B.68 1-(3-cyclopropoxymethyl-pyrrolidin)-yl-2,5-dione B.69 1-(3-isopropoxymethyl-pyrrolidin)-yl-2,5-dione B.70 1-(3-isobutoxymethyl-pyrrolidin)-yl-2,5-dione B.71 1-(3-allyloxymethyl-pyrrolidin)-yl-2,5-dione B.72 1-(3,3-dimethyl-pyrrolidin)-yl-2,5-dione B.73 1-(3,3-diethyl-pyrrolidin)-yl-2,5-dione

Table 30: Compounds of general formula (Id) wherein X₁ and X₂ are fluorine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 31: Compounds of general formula (Ie) wherein X₁ and X₂ are fluorine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 32: Compounds of general formula (If) wherein X₁ and X₂ are fluorine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 33: Compounds of general formula (Id) wherein X₁ and X₂ are fluorine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 34: Compounds of general formula (Ie) wherein X₁ and X₂ are fluorine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 35: Compounds of general formula (If) wherein X₁ and X₂ are fluorine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 36: Compounds of general formula (Id) wherein X₁ and X₂ are fluorine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 37: Compounds of general formula (Ie) wherein X₁ and X₂ are fluorine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 38: Compounds of general formula (If) wherein X₁ and X₂ are fluorine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 39: Compounds of general formula (Id) wherein X₁ and X₂ are chlorine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 40: Compounds of general formula (Ie) wherein X₁ and X₂ are chlorine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 41: Compounds of general formula (If) wherein X₁ and X₂ are chlorine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 42: Compounds of general formula (Id) wherein X₁ and X₂ are chlorine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 43: Compounds of general formula (Ie) wherein X₁ and X₂ are chlorine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 44: Compounds of general formula (If) wherein X₁ and X₂ are chlorine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 45: Compounds of general formula (Id) wherein X₁ and X₂ are chlorine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 46: Compounds of general formula (Ie) wherein X₁ and X₂ are chlorine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 47: Compounds of general formula (If) wherein X₁ and X₂ are chlorine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 48: Compounds of general formula (Id) wherein X₁ and X₂ are bromine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 49: Compounds of general formula (Ie) wherein X₁ and X₂ are bromine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 50: Compounds of general formula (If) wherein X₁ and X₂ are bromine and n is 2, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 51: Compounds of general formula (Id) wherein X₁ and X₂ are bromine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 52: Compounds of general formula (Ie) wherein X₁ and X₂ are bromine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 53: Compounds of general formula (Ie) wherein X₁ and X₂ are bromine and n is 3, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 54: Compounds of general formula (Id) wherein X₁ and X₂ are bromine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 55: Compounds of general formula (Ie) wherein X₁ and X₂ are bromine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Table 56: Compounds of general formula (If) wherein X₁ and X₂ are bromine and n is 4, and the substituent R for each compound corresponds to a line B.1 to B.73 of Table B.

Formulation Examples (%=Percent by Weight)

Example F1: Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate  5%  8%  6% castor oil polyethylene glycol ether (36 mol EO)  5% — — tributylphenol polyethylene glycol ether (30 mol — 12%  4% EO) cyclohexanone — 15% 20% xylene mixture 65% 25% 20%

Mixing finely ground active ingredient and additives gives an emulsifiable concentrate which yields emulsions of the desired concentration on dilution with water.

Example F2: Solutions a) b) c) d) active ingredient 80% 10%  5% 95% ethylene glycol monomethyl ether 20% — — — polyethylene glycol (MW 400) — 70% — — N-methylpyrrolid-2-one — 20% — — epoxidised coconut oil — —  1%  5% benzine (boiling range: 160–190°) — — 94% —

Mixing finely ground active ingredient and additives gives a solution suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d) active ingredient  5% 10%  8% 21% kaolin 94% — 79% 54% highly dispersed silicic acid  1% — 13%  7% attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated off in vacuo.

Biological Examples Example B1 Action Against Heliothis virescens Caterpillars

Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound. After the spray-coating has dried, the soybean plants are populated with 10 caterpillars of Heliothis virescens in the first stage and placed in a plastics container. Evaluation is made 6 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on the untreated plants.

The compounds of the Tables exhibit good activity against Heliothis virescens in this test. In particular, the compounds 1.3, 1.4, 1.6 and 1.10 are more than 80% effective.

Example B2 Action Against Plutella xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound. After the spray-coating has dried, the cabbage plants are populated with 10 caterpillars of Plutella xylostella in the third stage and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that, on the untreated plants.

The compounds of the Tables exhibit good activity against Plutella xylostella. In particular, the compounds 1.4 to 1.12 and 1.18 are more than 80% effective.

Example B3 Action Against Spodoptera littoralis

Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound and, after the spray-coating has dried, the plants are populated with 10 caterpillars of Spodoptera littoralis in the first stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

The compounds of the Tables exhibit good activity in this test. In particular, the compounds 1.3 to 1.7, 1.9 to 1.12 and 1.18 are more than 80% effective. 

1. A compound of formula

wherein A₁, A₂ and A₃ are each independently of the others a bond or a C₁–C₆alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl; A₄ is a C₁–C₆alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl; D is CH; T is a bond, O, NH, NR₇, S, SO, SO₂, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR₈— or —NR₈—C(═O)—; W is O, NR₇, S, SO, SO₂, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR₈— or —NR₈—C(═O)—; Q is O, NR₇, S, SO or SO₂; Y is O, NR₇, S, SO or SO₂; X₁ and X₂ are each independently of the other fluorine, chlorine or bromine; R₁, R₂ and R₃ are each independently of the others H, halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₁–C₆alkoxycarbonyl or C₂–C₆haloalkenyloxy; the substituents R₃ being independent of one another when m is 2; R₄ is H, halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₁–C₆alkoxycarbonyl or C₂–C₆haloalkenyloxy; the substituents R₄ being independent of one another when k is greater than 1; R₅ is H, CN, OH, C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, —C(═O)R₉, —C(═S)R₉, phenyl, benzyl; or phenyl or benzyl each of which is substituted in the aromatic ring by from one to five identical or different substituents selected from the group consisting of halogen, C₁–C₆alkyl, halo-C₁–C₆alkyl, C₁–C₆alkoxy, halo-C₁–C₆alkoxy, hydroxy, cyano and nitro; R₆ is H, CN, C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₆haloalkyl, —C(═O)R₉, —C(═S)R₉, phenyl, benzyl; or phenyl or benzyl each of which is substituted in the aromatic ring by from one to five identical or different substituents selected from the group consisting of halogen, C₁–C₆alkyl, halo-C₁–C₆alkyl, C₁–C₆alkoxy, halo-C₁–C₆alkoxy, hydroxy, cyano and nitro; or R₅ and R₆ together form a four- to eight-membered alkylene or a four- to eight-membered alkenylene bridge wherein a CH₂ group may have been replaced by O, S or NR₁₀, and the alkylene or alkenylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₃haloalkyl, CN and —C(═O)C₁–C₆alkyl; or R₆ is —C(═O)R₉ or —C(═S)R₉, and R₅ and R₉ together form a two- to eight-membered alkylene or a two- to eight-membered alkenylene bridge wherein a CH₂ group may have been replaced by O, S or NR₁₀, and wherein the alkylene or alkenylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₃haloalkyl, CN and —C(═O)C₁–C₆alkyl; or R₅ and R₆ are each independently of the other —C(═O)R₉ or —C(═S)R₉, and the two R₉ together form a two- to eight-membered, straight-chain or branched alkylene or a two- to eight-membered alkenylene bridge wherein a CH₂ group may have been replaced by O, S or NR₁₀; and wherein the alkylene or alkenylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C₁–C₆alkyl, C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl, C₁–C₃haloalkyl, CN and —C(═O)C₁–C₆alkyl; R₇ is H, C₁–C₆alkyl, C₁–C₃haloalkyl, C₁–C₃haloalkylcarbonyl, C₁–C₆alkoxyalkyl, C₁–C₆alkylcarbonyl or C₃–C₈cycloalkyl; R₈ is H, C₁–C₆alkyl, C₁–C₃haloalkyl, C₁–C₃haloalkylcarbonyl, C₁–C₆alkoxyalkyl, —C(═O)C₁–C₆alkyl or C₃–C₈cycloalkyl; R₉ is C₁–C₆alkyl, C₁–C₆haloalkyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₂–C₆alkenyloxy, C₂–C₆haloalkenyloxy, C₂–C₆alkynyloxy, C₃–C₆cycloalkyl, phenyl, benzyl; or phenyl or benzyl each of which is unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, C₁–C₆alkyl, C₁–C₆haloalkyl, C₁–C₆alkylcarbonyl, C₂–C₆alkenyl, C₂–C₆haloalkenyl, C₂–C₆alkynyl, C₁–C₆alkoxy, C₁–C₆haloalkoxy, C₁–C₆alkoxycarbonyl, C₁–C₃haloalkoxycarbonyl and C₂–C₆haloalkenyloxy; R₁₀ is H, C₁–C₆alkyl, C₁–C₃haloalkyl, C₁–C₃haloalkylcarbonyl, C₁–C₆alkoxyalkyl, C₁–C₆alkylcarbonyl or C₃–C₈cycloalkyl; k, or, when D is CH, is 1, 2, 3 or 4; and m is 1 or 2; and, where applicable, a possible E/Z isomer, E/Z isomeric mixture and/or tautomer thereof, in each case in free form or in salt form.
 2. A compound according to claim 1 of formula (I) in free form.
 3. A compound according to claim 1 of formula (I) wherein X₁ and X₂ are chlorine or bromine.
 4. A pesticidal composition which comprises as active ingredient at least one compound according to claim 1 of formula (I), in free form or in agrochemically acceptable salt form, and at least one adjuvant.
 5. A process for the preparation of a composition as described in claim 1 which comprises mixing the active ingredient, of formula 1, according to claim 1, with at least one adjuvant.
 6. A method of controlling pests which comprises applying a pesticidal composition as described in claim 1 to the pests or to the locus.
 7. A compound according to claim 3 in free form.
 8. A compound according to claim 1, wherein: A₂ is a bond; W is —C(═O)—NR₈; A₄ is a C₁–C₆alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from C₃–C₈cycloalkyl, C₃–C₈cycloalkyl-C₁–C₆alkyl and C₁–C₃haloalkyl; Q is O; and Y is O.
 9. A pesticidal composition which comprises as active ingredient at least one compound according to claim 8, in free form or in agrochemically acceptable salt form, and at least one adjuvant.
 10. A method of controlling pests which comprises applying a pesticidal composition as described in claim 9 to the pests or to the locus. 